CN103066321A - High capacity and high rate type soft-package lithium iron phosphate battery - Google Patents
High capacity and high rate type soft-package lithium iron phosphate battery Download PDFInfo
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- CN103066321A CN103066321A CN2013100051460A CN201310005146A CN103066321A CN 103066321 A CN103066321 A CN 103066321A CN 2013100051460 A CN2013100051460 A CN 2013100051460A CN 201310005146 A CN201310005146 A CN 201310005146A CN 103066321 A CN103066321 A CN 103066321A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a high capacity and high rate type soft-package lithium iron phosphate battery. The preparation method of the battery comprises the following steps: 1, anode material preparation: pulping lithium iron phosphate doped with Mg<2+>, a conductive agent and a binder in proportion, and coating the obtained pulp on an aluminum foil; 2, cathode material preparation: pulping an active substance, the conductive agent and styrene-butadiene rubber in proportion, and coating the obtained pulp on a copper foil; and 3, laminating to prepare the soft-package battery. The high rate discharge performance of the battery is improved by increasing the conductivity of lithium iron phosphate through doping lithium iron phosphate with Mg<2+> in the preparation method. The battery adopts a lamination structure, and tabs are welded through adopting large-power ultrasonic welding, so internal resistance benefiting and rate discharge performance improvement are realized. The continuous discharge current of the battery can reach 10C, and the capacity conservation rate of the battery can reach 90% of a rated capacity.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of large capacity high magnification type Soft Roll ferric phosphate lithium cell and preparation method thereof.
Background technology
Along with the continuous minimizing of traditional non-renewable energy and going from bad to worse of environmental problem, human more and more urgent to research and development of new sources of energy.Lithium ion battery becomes one of study hotspot in recent years with advantages such as its high-energy-density, energy-efficient, environment friendly.
Distinguish with positive electrode, lithium ion battery is divided into cobalt acid lithium battery, lithium manganate battery, ternary material battery, ferric phosphate lithium cell etc., and wherein, cobalt acid lithium battery occupies main status in the portable type electronic product field; LiFePO4 has a extensive future at large-sized power battery and energy storage field with its Stability Analysis of Structures, pollution-free, the advantage such as fail safe good, the life-span is long.
Because pure electric automobile, hybrid vehicle, electric tool etc. have higher requirement to the high rate performance of battery, the present invention has developed a kind of high magnification type Soft Roll ferric phosphate lithium cell.
Summary of the invention
The objective of the invention is to develop a kind of large capacity high magnification type Soft Roll ferric phosphate lithium cell, solve the poor problem of common high rate discharge for lithium ion battery.
A kind of large capacity high magnification type Soft Roll ferric phosphate lithium cell, the preparation method of the positive and negative pole material of described battery comprises:
Positive electrode is with doped with Mg
2+LiFePO4, conductive agent and binding agent be coated on the aluminium foil after the slurrying in proportion; Doped with Mg wherein
2+LiFePO4, accounting for percentage by weight is 85-92%, conductive agent is carbon black conductive agent or graphite agent, such as super-P or KS series, accounting for percentage by weight is 2-5%; Binding agent is Kynoar series, and accounting for percentage by weight is 3-10%; The LiFePO4 doped with Mg is taked in the positive electrode preparation
2+Method, to improve the conductivity of material, improve high rate performance.
Negative material is that active material, conductive agent and butadiene-styrene rubber are coated on the Copper Foil after the slurrying in proportion, and wherein active material is MCMB (MCMB) or graphite or lithium titanate or silicon carbon compound, and accounting for percentage by weight is 90-95%; Conductive agent is carbon black conductive agent or graphite agent, and such as one or more the mixing in super-P or KS series, carbon nano-tube (CNTs) and the carbon nano-fiber (VGCF), accounting for percentage by weight is 1-3%; It is 2-7% that butadiene-styrene rubber accounts for weight percent.
Shown in battery be to make soft-package battery in the lamination mode.
Battery of the present invention, wherein said doped with Mg
2+LiFePO4, be by Li
1-xMg
xFePO
4Stoichiometric proportion take by weighing LiOHH
2O, MgO, FePO
4, add an amount of absolute ethyl alcohol ball milling and mix, then at N
2The lower 700 ℃ of roasting 12h of atmosphere are with the preparation doped with Mg
2+LiFePO4, x=0.005-0.02 wherein.
Battery of the present invention carries out under humidity≤10%RH during wherein said battery assembling, adopts the lamination mode to make soft-package battery, and tab welding adopts the high-power ultrasonics welding.
Battery of the present invention, wherein said positive pole aluminium foil thickness are 15-25 μ m, and negative copper foil thickness is 12-20 μ m; Anode ear is aluminium strip, thickness 0.2-0.3mm, width 20-60mm; Negative electrode lug is copper nickel plating, thickness 0.2-0.3mm, width 20-60mm; Aluminum plastic film thickness is 0.153mm.
Battery of the present invention, wherein said battery diaphragm adopts PP/PE/PP sandwich diaphragm or PE barrier film or PP barrier film; Electrolyte is one or more the mixture in lithium hexafluoro phosphate and methyl ethyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, the propene carbonate.
The preparation method of battery of the present invention may further comprise the steps:
(1) anodal preparation: at first binding agent is dissolved in the organic solvent n-formyl sarcolysine base pyrrolidones mixing speed 50r/min, high speed dispersion speed 1500r/min, time 4h; Add again the doped with Mg that is pre-mixed
2+LiFePO4 and conductive agent, high speed dispersion speed 1800r/min, time 5h obtains slurry; Slurry viscosity is controlled at 5000-10000mPa.s; Be coated on the aluminium foil with automatic coating machine;
(2) negative pole preparation: at first sodium carboxymethylcellulose is dissolved in deionized water, adds butadiene-styrene rubber, mixing speed 40r/min, high speed dispersion speed 1500r/min, time 4h; Add again negative electrode active material and the conductive agent that is pre-mixed, mixing speed 60r/min, high speed dispersion speed 1500r/min, time 4h; Be coated on the Copper Foil with automatic coating machine;
(3) the both positive and negative polarity pole piece is put into the vacuum drying oven baking after punching, every 4h inflated with nitrogen ventilation, and vacuum degree≤-0.09MPa; Be assemblied under humidity≤10%RH environment and carry out, adopt the high-power ultrasonics soldering polar ear, adopt the lamination mode to make soft-package battery.
Fluid injection behind the battery core baking 48h in the described step (3), change into, partial volume, electrolyte is LiPF
6The organic solution system, barrier film adopts three layers of composite diaphragm of PP/PE/PP, membrane thicknesses 30 μ m.
Battery of the present invention and preparation method thereof possesses following advantage:
1. pass through the LiFePO4 doped with Mg
2+Improve the conductivity of material, improved high-rate discharge ability.
2. churned mechanically method is taked in both positive and negative polarity slurrying; Be assemblied under humidity≤10%RH environment and carry out, adopt the high-power ultrasonics soldering polar ear, increase weld strength, be conducive to high-rate battery discharge; Battery adopts laminated structure, and tab welding adopts the high-power ultrasonics welding, is conducive to reduce internal resistance, improves multiplying power discharging property.
3. adopt the battery of this method preparation, its continuous discharge electric current can reach 10C, and capability retention reaches 90% of rated capacity.
Description of drawings
Fig. 1 is the battery positive and negative plate design shape figure of the embodiment of the invention 1;
Fig. 2 is the battery design shape figure of the embodiment of the invention 1;
Fig. 3 is the multiplying power discharging curve of embodiment 1HPPF11198141/3.2V/20Ah battery;
Fig. 4 is the battery positive and negative plate design shape figure of the embodiment of the invention 2;
Fig. 5 is the battery design shape figure of the embodiment of the invention 2;
Fig. 6 is the multiplying power discharging curve of embodiment 2HPPF80173248/3.2V/20Ah battery.
Embodiment
For further specifying the present invention, specify with the following Examples:
Embodiment 1
Described battery specifications and models are HPPF11198141/3.2V/20Ah.
The below illustrates as an example of the preparation process of HPPF11198141/3.2V/20Ah battery example, battery appearance and pole piece as illustrated in fig. 1 and 2, battery production method is as follows:
Positive active material preparation: press Li
1-xMg
xFePO
4(x=0.005-0.02) stoichiometric proportion takes by weighing LiOHH
2O, MgO, FePO
4, add an amount of absolute ethyl alcohol ball milling and mix, then at N
2The lower 700 ℃ of roasting 12h of atmosphere are with the preparation anode active material of phosphate iron lithium.
Anodal preparation: doped with Mg
2+LiFePO4, super-P, KS-6, PVDF900(Vingon), the mass ratio of n-formyl sarcolysine base pyrrolidones (NMP) is 90:3:2:5:112.At first PVDF900 is dissolved in NMP, mixing speed 50r/min, high speed dispersion speed 1500r/min, time 4h; Add again LiFePO4 and the conductive agent that mixes, high speed dispersion speed 1800r/min, time 5h, slurry viscosity is controlled at 5000-10000mPa.s; With automatic coating machine coating, aluminum foil thickness 20 μ m, coated side density 240g/m
2
Negative pole preparation: MCMB, super-P, SBR(butadiene-styrene rubber), carboxycellulose sodium (CMC), the mass ratio of deionized water are 91:3:4:2:120; At first CMC is dissolved in deionized water, adds SBR, mixing speed 40r/min, high speed dispersion speed 1500r/min, time 4h; Add again negative electrode active material and the conductive agent that is pre-mixed, mixing speed 60r/min, high speed dispersion speed 1500r/min, time 4h; With automatic coating machine coating, copper thickness 15 μ m, coated side density 10
8G/m
2
The both positive and negative polarity pole piece is put into the vacuum drying oven baking after punching, every 4h inflated with nitrogen ventilation, and vacuum degree≤-0.09MPa; Be assemblied under humidity≤10%RH environment and carry out, adopt the high-power ultrasonics soldering polar ear, adopt the stacked soft-package battery of making.Fluid injection behind the battery core baking 48h, change into, partial volume, reservoir quantity 120g, electrolyte are LiPF
6The organic solution system, barrier film adopts three layers of composite diaphragm of PP/PE/PP, membrane thicknesses 30 μ m.
The preparation the battery high-rate discharge ability as shown in Figure 3, its 10C discharge capacity reaches more than 90% of rated capacity.
Described battery specifications and models are HPPF80173248/3.2V/20Ah.
The below illustrates as an example of the preparation process of HPPF80173248/3.2V/20Ah battery example, battery appearance and pole piece as shown in Figure 4 and Figure 5, battery production method is as follows:
Positive active material preparation: press Li
1-xMg
xFePO
4(x=0.005-0.02) stoichiometric proportion takes by weighing LiOHH
2O, MgO, FePO
4, add an amount of absolute ethyl alcohol ball milling and mix, then at N
2The lower 700 ℃ of roasting 12h of atmosphere are with the preparation anode active material of phosphate iron lithium.
Anodal preparation: doped with Mg
2+LiFePO4, super-P, KS-6, PVDF900(Vingon), the mass ratio of n-formyl sarcolysine base pyrrolidones (NMP) is 91:3:1:5:112.At first PVDF900 is dissolved in NMP, mixing speed 50r/min, high speed dispersion speed 1500r/min, time 4h; Add again LiFePO4 and the conductive agent that mixes, high speed dispersion speed 1800r/min, time 5h, slurry viscosity is controlled at 5000-10000mPa.s; With automatic coating machine coating, aluminum foil thickness 20 μ m, coated side density 240g/m
2
Negative pole preparation: MCMB, super-P, SBR(butadiene-styrene rubber), carboxycellulose sodium (CMC), the mass ratio of deionized water are 92:3:4:1:115; At first CMC is dissolved in deionized water, adds SBR, mixing speed 40r/min, high speed dispersion speed 1500r/min, time 4h; Add again negative electrode active material and the conductive agent that is pre-mixed, mixing speed 60r/min, high speed dispersion speed 1500r/min, time 4h; With automatic coating machine coating, copper thickness 15 μ m, coated side density 10
8G/m
2
The both positive and negative polarity pole piece is put into the vacuum drying oven baking after punching, every 4h inflated with nitrogen ventilation, and vacuum degree≤-0.09MPa; Be assemblied under humidity≤10%RH environment and carry out, adopt the high-power ultrasonics soldering polar ear, adopt the stacked soft-package battery of making.Fluid injection behind the battery core baking 48h, change into, partial volume, reservoir quantity 120g, electrolyte are LiPF
6The organic solution system, barrier film adopts three layers of composite diaphragm of PP/PE/PP, membrane thicknesses 30 μ m.
The preparation the battery high-rate discharge ability as shown in Figure 6, its 10C discharge capacity reaches more than 90% of rated capacity.
Above-described embodiment is described preferred implementation of the present invention; be not that scope of the present invention is limited; design under the prerequisite of spirit not breaking away from the present invention; various distortion and improvement that the common engineers and technicians in this area make technical scheme of the present invention all should fall in the definite protection range of claims of the present invention.
Claims (7)
1. large capacity high magnification type Soft Roll ferric phosphate lithium cell, it is characterized in that: the preparation method of the positive and negative pole material of described battery comprises:
Positive electrode is with doped with Mg
2+LiFePO4, conductive agent and binding agent be coated on the aluminium foil after the slurrying in proportion; Doped with Mg wherein
2+LiFePO4, accounting for percentage by weight is 85-92%, conductive agent is carbon black conductive agent or graphite agent, accounting for percentage by weight is 2-5%; Binding agent is Kynoar, and accounting for percentage by weight is 3-10%;
Negative material is that active material, conductive agent and butadiene-styrene rubber are coated on the Copper Foil after the slurrying in proportion, and wherein active material is MCMB or graphite or lithium titanate or silicon carbon compound, and accounting for percentage by weight is 90-95%; Conductive agent is carbon black conductive agent or graphite agent, and accounting for percentage by weight is 1-3%; It is 2-7% that butadiene-styrene rubber accounts for weight percent;
Described battery is made soft-package battery in the lamination mode.
2. battery according to claim 1 is characterized in that: described doped with Mg
2+LiFePO4, be by Li
1-xMg
xFePO
4Stoichiometric proportion take by weighing LiOHH
2O, MgO, FePO
4, add an amount of absolute ethyl alcohol ball milling and mix, then at N
2The lower 700 ℃ of roasting 12h of atmosphere prepare doped with Mg
2+LiFePO4, x=0.005-0.02 wherein.
3. battery according to claim 1 is characterized in that: carry out under humidity≤10%RH during described battery assembling, adopt the lamination mode to make soft-package battery, the welding of tab welding employing high-power ultrasonics.
4. battery according to claim 1, it is characterized in that: described positive pole aluminium foil thickness is 15-25 μ m, negative copper foil thickness is 12-20 μ m; Anode ear is aluminium strip, thickness 0.2-0.3mm, width 20-60mm; Negative electrode lug is copper nickel plating, thickness 0.2-0.3mm, width 20-60mm; Aluminum plastic film thickness is 0.153mm.
5. battery according to claim 1 is characterized in that: described battery diaphragm employing PP/PE/PP sandwich diaphragm or PE barrier film or PP barrier film, thickness 20-60 μ m; Electrolyte is one or more the mixture in lithium hexafluoro phosphate and methyl ethyl carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, the propene carbonate.
6. the preparation method of each described battery of claim 1-5 is characterized in that: may further comprise the steps:
(1) anodal preparation: at first binding agent is dissolved in the organic solvent n-formyl sarcolysine base pyrrolidones mixing speed 50r/min, high speed dispersion speed 1500r/min, time 4h; Add again the doped with Mg that is pre-mixed
2+LiFePO4 and conductive agent, high speed dispersion speed 1800r/min, time 5h obtains slurry; Slurry viscosity is controlled at 5000-10000mPa.s; Be coated on the aluminium foil with automatic coating machine;
(2) negative pole preparation: at first sodium carboxymethylcellulose is dissolved in deionized water, adds butadiene-styrene rubber, mixing speed 40r/min, high speed dispersion speed 1500r/min, time 4h; Add again negative electrode active material and the conductive agent that is pre-mixed, mixing speed 60r/min, high speed dispersion speed 1500r/min, time 4h; Be coated on the Copper Foil with automatic coating machine;
(3) the both positive and negative polarity pole piece is put into the vacuum drying oven baking after punching, every 4h inflated with nitrogen ventilation, and vacuum degree≤-0.09MPa; Be assemblied under humidity≤10%RH environment and carry out, adopt the high-power ultrasonics soldering polar ear, adopt the lamination mode to make soft-package battery.
7. preparation method according to claim 6 is characterized in that: fluid injection behind the battery core baking 48h in the described step (3), change into, partial volume, electrolyte is LiPF6 organic solution system, barrier film adopts three layers of composite diaphragm of PP/PE/PP, membrane thicknesses 30 μ m.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367754A (en) * | 2013-07-29 | 2013-10-23 | 河南环宇赛尔新能源科技有限公司 | Soft-package aqueous lithium iron phosphate power battery and making method thereof |
| CN103390780A (en) * | 2013-08-15 | 2013-11-13 | 刘洪� | Environment-friendly iron phosphate magnesium lithium battery and preparation method thereof |
| CN105304857A (en) * | 2015-09-25 | 2016-02-03 | 河南环宇赛尔新能源科技有限公司 | Soft-package lithium iron phosphate battery |
| CN105870443A (en) * | 2016-04-28 | 2016-08-17 | 深圳市力为锂能科技有限公司 | Lithium iron phosphate composite material and preparation method thereof |
| CN109994769A (en) * | 2017-12-30 | 2019-07-09 | 程艳青 | A kind of large-capacity high-power start and stop ferric phosphate lithium cell manufacturing method |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103367754A (en) * | 2013-07-29 | 2013-10-23 | 河南环宇赛尔新能源科技有限公司 | Soft-package aqueous lithium iron phosphate power battery and making method thereof |
| CN103390780A (en) * | 2013-08-15 | 2013-11-13 | 刘洪� | Environment-friendly iron phosphate magnesium lithium battery and preparation method thereof |
| CN105304857A (en) * | 2015-09-25 | 2016-02-03 | 河南环宇赛尔新能源科技有限公司 | Soft-package lithium iron phosphate battery |
| CN105870443A (en) * | 2016-04-28 | 2016-08-17 | 深圳市力为锂能科技有限公司 | Lithium iron phosphate composite material and preparation method thereof |
| CN105870443B (en) * | 2016-04-28 | 2018-11-09 | 深圳市力为锂能科技有限公司 | A kind of composite ferric lithium phosphate material and preparation method thereof |
| CN109994769A (en) * | 2017-12-30 | 2019-07-09 | 程艳青 | A kind of large-capacity high-power start and stop ferric phosphate lithium cell manufacturing method |
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|---|---|
| CN103066321B (en) | 2016-05-04 |
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